Production of useful materials



Nov. 2l, `1944.

J. E. HARVEY, JR

PRODUCTION OF USEFUL MATERIALS Filed oct, 91.1942

.ifea/va cam/mm1 50M-M' armar/wy is theiinduction l Prasad Nov: 21, 1944raoDUc'rroN or USEFUL MATERIALS t Jacquelin E. Harvey, Jr-.,

signor of one-half to S lng Cinpany, East Po Geor Washington, D. C.,asouthern Wood Preservint, Ga., a corporation of Application October 9,1942, .Serial No. 461,500

4 claims. (c1. 19H9) The instant invention relates to th'e production oftoxic oils employable as fungicides, insecticides, and for any otherservice' to which toxic oils may be put.

More especially the instant invention relates to the productionV oftoxic oils from mixtures of petroleum fractions characterized by ringstructure content. Among such starting materials may be mentionedmixtures) of petroleum fractions characterized by ring structure contentrecovered from petroleum fractions by well known extraction methodsincluding extractiva distillation and azeotrcpic distillation. Also maybe mentioned mixtures of petroleum fractions characterized by ringstructure content as owing from thermal and-or catalytic treatment ofcertain petroleum fractions which includes petroleum fractions havingring structures induced in the course of thermal and/or catalytictreatment, as for example having ring structures induced in the courseof one or more thermal and/croatalytic treatments of unusual length, asfor example, for periods of 1-10 hours or more.

An object of the instant invention is the production of toxic oils fromthe aforenamed petroleum fractions or others whereby to provide Voils ofthepreservative type, as for example preservative wood impregnantsconforming to specifications extant or acceptable to the trade consumingsuch oil materials.

Another object of the instant invention is the provision of preservativewood impregnants having evaporation rates under given conditionsacceptable to the trade.

Another object of the instant invention is the reforming of the abovenamed mixtures of hydrocarbons or others whereby to induce toxicity.

Still another object of the instant invention is the induction of usabletoxicity in the p1" enceof a gas or gaseous mixtures.

' Yet another object of the instant invention of toxicity in the abovenamed mixtures of petroleum fractions or others, the while or afterwardsproviding specific means which guard against diminution in saidVVtoxicity.

Another object of the instant invention is the release of latent`toxicity in the above named mixtures of petroleum fractions or others.

Another object of the instant invention'is 'the release of latenttoxicity in the above named mixtures of petroleum fractions or othersbyh in-` creasingl the water solubility of said materials.

Other objects of the instant invention will be apparent as flowing fromthe following disclosures and examples.

In the past wood preservative oils of 'the high temperature coal tarderived type have been employed in quantities greatly exceeding thetotal of all other wood preservative oils. From the standpoint ofavailability of said coal taras 'the parent material of woodpreservative oils,

it is annually produced in this country under f normal conditions to theextent of live hundred million to six hundred million gallons,` Thisquantity of coal tar is capable of yielding an amount of highlyellective wood preservative oils which would make this country selfsuflicient in its wood preservative requirements. However, due to thefact that when a wood preservative distillate (creosote) is recoveredfrom coal tar there remains in the still a. residue (pitchl which,

at best, is a. lowpriced product and which, at Worst, is a seriouslydistress product to the end that at times it is placed in inventoryrather than sold, the current method of processing coal tar leaves muchto be desired. The net result of this situation obtaining is that thecoal tar distiller usually confines himself to that distillationrecovery of creosote which would. correspond to the attending amount ofpitch that he can market at a prot. Accordingly, over a period of yearssevera-l hundred million gallons of creosote oil have beenimported intothis country. That such a situation should obtain is apparently aparadox in that we annually produce a quantity of high temperature coaltarl which if processed to yield creosote would make us self sufficientin that requirement. A survey of this paradox is fully outlined in anaddress given by no less an authority than S. P. Miller, technicaldirector, The Barrett Company, 4U Rector Street, New York city, beforethe Franklin Institute, Philadelphia, Pennsylvania, in Decemt ber, 1932.'Ihe economics of coal tar have not materially changed since that date.

In view of the apparent inability of the coal tar industry to, providenational needs of wood preservative oils, a strong incentive is given togroups Processing other types of oil to :invade the lucrative woodpreservative market. At the present time many types of aromatic oils areproduced vbythe petroleum industry, and the high boiling oils ofaromaticv content produced by this industry have for several years beentested for their wood preservative efficiency.

`By the term petroleum aromaticv as used herein and in the appended`claims is meant to include mixtures of petroleum fractionscharacterized by cyclic content and includes specifically various formsand types of naphthenes found in However, very little work has been doneon thesev materials. Such `a fact is borne outon page 667 v fReactionsof pure hydrocarbons Gustav Egloif,

Reinhold, Publishing Corporation, 330 West 42nd Street, New York city,which states:

Despite the fact that naphthenes or cycloparaines are available inenormous quantities, as shown by an` estimate of, 100,000,000 barrelspresent in the 1,498,000,000 barrels of crude oil which was the Worldsproduction in 1934, comparatively little work of a pyrolytic nature hasbeen performed on individual naphthene hydrocarbons 'or the cycloolens.

Several oils of cyclic content produced by the petroleum industry havebeen inspected for their toxicity'to wood destroying fungi, among whichy may be mentioned a high boiling oil of cyclic content produced (1940,)at the Wood River renery of the Shell Oil Company and which has thefollowing inspection:

Gravity 10.8 Flash, P. M. C. C I F 295 Flash, C. O. C. ...l F 290 Fixedcarbon L per cent-- 4.9 Pour point F -10 B. S. & W per cent by volume-0.1 S. U. vis. v100" F 151 S. U..vis. (d) 210 F 41 S. F. vis. 77 F 34.5Carbon residue 6.8 y Per cent aromatics and unsaturates 82.4 Sol. in CS299.8 Loss. 50 grams, 5 hours, 325 F 8.9 Residue of 100 pene per cent37.5 A. S. T. M. distillation:

I.B. P F 518 10% rec. F 565 20% rec. 'F 589 30% rec. F 614 40% rec. F637 50% rec. F 660 60% rec. F 1 675 1Maximum.

In the foregoing tabular data P. M. C. C. means Pensky- Martin ClosedCup; C. 0. C. means Cleveland Open Cup..

Upon evaluating the foregoing oil for its toxicity to wood destroyingfungi (Madison 517), it was found that this oil did not inhibit thegrowth of the fungi named at a concentration of up to and including 10%.

It is now discovered that the oil above named or other oils of cycliccontent produced by the petroleum industry can be increased in toxicityin accordance with the process of the instant invention.

According to the instant invention oils of cyclic content produced bythe petroleum industry are reformed, transformed. modi'ed and/orconverted to oils of a more toxic nature having charcal and chemicalcharacteristics which to a great degree indicate that the new productwould have good life service after its impregnation into the materialtolbe preserved.

The following examples will illustrate several modes of practicing theprocess of the present invention. The single g`ure of thedrawingrepproduced by well known extraction methods isv (1) subjected to athermal and/0r catalytic treat# ment at a relatively high pressure andthereafter 2) subjected to further thermal and/or catalytic treatment ata relatively low pressure whereby to provide a newly formed oil havingless than 30% but more than 5%, and preferably more than 10% saturatesin the materials boiling between 270 C. and 355 C., the finallyconverted material is adapted to yield an oil of the wood preservativetype characterized by induced toxic properties,v substantial residualmatter above 315 C. or 355 C. and a specific gravity falling between thelimits of 0.85 and 1.10, preferably between 0.95 and 1.05.

Example 1.A mixture of petroleum fractions characterlzed by cycliccontent selected from the group consisting of aromatic extracts,extractive distillates, azeotropic distillates and fractions havinginduced cyclic structures as flowing from thermal and/or catalyticaction. repeated or otherwise, as for example an aromatic extract of amixture of high boiling petroleum Ifractions. said extract boilingentirely above 240 C., characterized by more than 30% saturates in` thematerials boiling between 270 C. and 355 C. and relatively littletoxicity is reformed, modified and/or converted by the present processand toxicity induced therein.

According to the process of the present invention the feed stockis-reformed. modified and/or converted in the liquid phase at atemperature selected between the limits of 400-600" C., as for exampleat a temperature of 450 C. whilst under a pressure of 1.000 pounds for aperiod of 30 minutes. The partially beneflciated material is passed toa-second treating zone where without substantial reduction intemperautre it is maintained at a pressureof 500 pounds for a period of30 minutes.

The beneiiciated material is cooled and inspected. and found to haveless than 30% but more than 5% saturates in the 270-355 C. fraction andasubstantial percentage of newly formed Vfractions boiling below 210 C.The oil is also bilized to provide a residual as an oil of the woodpreservative type having induced toxic properties, about 5% boiling at210 C. and in excess of 5% boiling above 355 C.

Other things being equal, the toxicity of a preservative oil isproportional to its percentage of unsaturates, that is to say, as thePercentage of unsaturates increases, the toxicity of the preservativebecomes more pronounced. It is well understood in the art that thematerials in a preservative impregnant boiling between 270 C. and 355 C.are among the least toxic. However, it is discovered that if an attemptis made to convert the entiretyof the materials boiling between 270 C.and 355 C. into unsaturates, reactions take place that' are prejudicialto the conversion of 'aseaaav the oil `to toxic substances, as forexample there occurs inordinate gasification and/or reformed highboilingmaterials that approach fixed car:

bon as anupper limit.

It is, therefore, an important part of the present process to so controland coordinate the reforming, modifying and/or converting action in bothof the process steps as to provide a treated 4,

material having less than 30% but more than 5%, andpreferably more than10% saturates in the fraction boiling between 27.0 C. and 355 C. Suchacontrol of saturates in the named fraction has the eiect of makingtoxicity more pronounced while at the same Atime obviationg theoperating ills above mentioned.

Example 2,-A mixture of petroleum fractions boiling prependerantly above210 c. having substantial residual matter above 355 C. charactel-ized bycyclic structures and relatively little toxicity is charged to apressure vessel and maintained at a'temperature of 440 C. whilst under apressure of 2,000 pounds for a period of 25 minutes. At the end of thenamed period thefraction less than 25% but more than 5% saturation.Further inspection discloses that the material has induced toxicity. Theoverall beneciated material is fractionally distilled to provide adistillate as an oil of the wood preservative type characterized byinduced toxic properties boilingL 11/2% at 235 C.and with 15% boilingabove 355 C.

'I'he wood preservative wimpregnant of the presi ent process which isrecovered from the overall processed oil is not circumscribed by anysingle boiling limitation, but is rather circumscribed by published woodpreservative specifications and/or the preference and acceptance of woodpreservative consumers. g

Accordingly, after the stated. oilshave been processed to providematerials of induced toxic properties in the manner stated herein, thepreservative impregnant may be segregated from the benefited material toprovide a residual, distillate or extract which conforms to any of thefollowing published woodpreservative specifications:

Woon Passsnvmo IMPxrlcNAN'rs i Specifications 1. American Wood4Preservers Association a. Up to 210 C., not-more than 5% b. Up to 235C., not more than 25% 2. American Wood Preservers Association a. Up to210 C., not more than 1% b. Up to 235 C., not more than 10% c. Up to 355C., not less than 65% 4. American Wood Preservers Association a. Up to210 C., not more than 8% b. Up to 235 C., not more than 35% 5. AmericanWood Preservers Association a. Up to 210 C., not more than 10% b. Up to235 C., not more than 40% 6. American Wood Preservers Association a. Upto 210 C., not more than 5% b.' Up to235 C., not more than 15% 7.Prussian Ry. d. Up to 150 C., not more than 3% b. Up to 200 C., not morethan 10% c. Up to 235 C., not more than 25% 8. National Paint lVarnishand Lacquer Association #220 a. 5% at 162 C. b. 97% et 270 c.

9. Southern pine shingle stain oil a. 5% at 137 C.

b. at 257 C.

v1o. Neville shingle stein ell a. I. B. P., C. I b. 5% at 205 C. c. 95%at292 C.

11. orbelmeum -.-270 c., I. B. P.

rapidly brought up to a temperature of 445 C. lwhilst under a-pressureof 1800 pounds. The

thus heated material isdischarged to a vessel4 where it is held under atemperature `of substantially 455 C. whilst in the presence of water gasat a pressure of 1200 pounds for a period of one hour. At the end ofythe hour period` the treated material is cooled and ,inspected and foundto have induced toxic properties. It is also found that a substantialpercentage of fractions boiling below 210 C. has been inducedand thatthe materials boiling between 27o-355 C. have less than 25% but morethan 5% saturates.

The material of induced toxic properties is then stabilized to provide aresidual as an oil of the wood preservative type characterized byinduced toxic properties, boiling 1% below 210 C. and having in excessof 10% materials boiling above 315 C.

Instead ofemploying water Vgas as the extraneous gas, hydrogen may beemployed and the partial pressure of the gases may be 5-50% or more.Also employable as extraneous gases are methane and its homologues,various reiinery gases, inert gases such as nitrogen and 4thosecontaining carbon. Various purposes are accomplished by the employmentof the gas of 'traneous source in both tioned, the thermal protection ofthe material undergoing reformation, conversion, transformation and/ormodification in order'to avoid excess carbonaceous deposits and/orconversion of fractional parts of the material to forms that aresubstantially non-toxic. If a gas reactive under the process conditionsis employed, this gas may also` assist in 'the accomplishing of thestated purpose orothers. The employment of the extraneous gas yor gasesnoted. separately or in admixture, are to be in one mode of operation,specifically read into all examples in either or both of the processsteps. now from the employment of the gas of exof the process steps, butgas in only one step has toxicity induction, as for the employment ofthea partial benefit toward example by employing Particular benefits thegas .of extraneous` source in the final step above noted which ischaracterized by a reduction in pressure.

Example 4.-A furfural extract of high boiling petroleum fractions, saidextract boiling entirely above 250 C. having substantial residual matterabove 355 C. and relatively little toxicity is passed through a seriesof tubes set in a furnace and rapidly brought up to a temperature of 470C. whilst under a pressure of 2500 pounds. The thus seated material isdischarged to an enlarged vessel and held at a temperature ofsubstantially {15G-460 C. whilst under a pressure of 1500 pounds for aperiod of one hour.

The overall beneflciated material is fractionally distilled to recover adistillate as arr'oil of the wood preservative type characterized byinduced toxic properties boiling 90% between 210 C. and 355 C. l

Inspection of the preservative distillate dis-` closes that the 27o-355C. fraction has more than 5% but less than 30% saturates.

Example 5.-A flashed petroleum residuum boiling entirely above 270 C.and With/ substantial residual matter above 355 C; characterized bycyclic structures and. relatively little toxicity is passed through a'series of tubes set in a furnace andrapidly brought up to a temperatureof 430 C. whilst under'a pressure of 750 pounds. Thereafter, the heatedmaterial is discharged into an enlarged zone and maintained at apressure of 300 pounds where without substantial reduction oftemperature it is held forxsuch a period as to' provide more than 5% butless than 25% .saturation in the 270-355 C. fraction.

The heat treated material is fractionally distilled `to recoveradistillate having substantially no ends boiling below 200 C. and with75% boiling up to 315 C. Upon inspection of the dis- Itillate it isfound to have toxic properties in excess `of the parent feed stock.

Instead of recovering the oil of the instant process as a distillate orstabilized residual, the overall beneciated oil may be extracted with asuitable solvent, as for' example with phenol, furfural, liquid lsulfurdioxide, cresol, xylol, cresylic acid, aniline, nitrobenzene,chloroaniline. nitrotoluene or the like. After thebeneciated materialhas been extracted the raflinate is then discarded. The solventisxremoved from the ,extract and the preservative oil of the instantprocess recovered from the extract as a stabilized I residual or aldistillate. However, if the extract has a boiling range in accordancewith published wood preservative specifications tabulated in theforegoing, the overall extract may be used as the oil of the instantprocess.

Example 6.--A petroleum oil of induced cyclic structures boilingpreponderantly above 210 C.,

having' in excess of 20% residual matter boiling above 355 C. andrelatively little toxicity is brought up to a temperature of 450 C.whilst under a pressure of 3,000 pounds and held at that temperature fora period of 30 minutes.

atively low toxicity as compared to materials boiling below thattemperature. The beneficiated material is cut at a temperature of 270 C.and the high boiling materials heat treated at a temperature of 440 C.whilst under a pressure of 3,000 pounds for a period of 20 minutes.After the 20 minute period the material is discharged into an enlargedzone Where it is held without a substantial reduction of temperatureunder a pressure of 2,000 pounds for a period of 20 minutes. o

The thus heat treated residual is commingled with the once beneficiatedfractions boiling below 270 C. whereby to provide an overallcomminglement having a toxicity in excess of the.

overall once beneficiated oil. The commingledmaterials are fractionallydistilled to recover a distillatey as an oil of the wood preservative"type characterized by induced toxic properties having` about 3%distilling below 150 C., substantial residual matter boiling above 355C. and less than but more than 5% saturates in the materials boilingbetween 270 C. and 355 C.

- Instead of retreating the entirety of the materials boiling above 270C. only a portion thereof may be retreated and 'certain toxicitybenefits'will flow therefrom.

Instead of commingling the entirety of the retreated residual and theentirety of the temporarily discarded and once treated low boilingfractions, only a portion of these two materials may be commingled,lprovided that the conimingled fractional parts provide the desiredpreservative oil or furnish an oil capable of yielding the desiredpreservative impregnant.

The temperatures employable in the process steps are lselected betweenthe limits of 350- 600 C., and preferably between 40o-500 6. 4 Thepressures in the first step of the process are in excess of atmosphericand are` preferably inexcess of 20 atmospheres, say pressures selectedbetween the-limits of 50-200 atmospheres. However, pressures as rhigh aspracticable may be employed. In the second step of the process,pressures in excess of atmospheric l `are generally preferred. However,in the event,

it is elected to operate the lfirst and relatively high pressure stepat, say a pressure of from 5 to 50 atmospheres, the relatively lowpressure in the second step may be at atmospheric pressure, or below ifdesired.

The time element of the instant process is so coordinated with theoverall pressures in both steps, the relative reduction of pressure inthe second step and thev temperatures in both steps as to provide in the270-355" C. fraction of the overall finally beneflciated material asaturation less than 30% but more than 5%. A few trials withany selectedstarting material will enable those skilled in the art to provide thecorrect coordination.

Various catalysts assist in the heat treating of the starting petroleumvoils whereby to provide induced toxic properties. These catalysts areemployable in either the vapor phase or the liquid phase, or both, andthis provision may in one mode of operation be specifically read intoeither or both of the steps of all examples.

Among such catalysts may be mentioned the various metals, their oxides,sulfides and carbonates, cellulosic materials and carbon, acti- Vated orotherwise. Various silicious materials including the various claysshaped or prepared Y in appropriate form may also be employed. Varioussynthetic gels, as for instance the well y A :,aoaaav known hydrogelsmay be employed as catalytic" materials including speciiically cipitatesproperly prepared.

gelatinous pre- Also employable are halogens, halids and derivativesthereof, in- Y cluding speciilcally substitution and addition productsthereof, as for example and speciilcally substitution and additionproducts of said derivatives, say a hydrogen halid or the like.

These catalytic materials above mentioned are eiective in promoting theprovision of the oils of the wood preservative type having induced toxicproperties and these catalytic materials separately, in admixture or twoor more employed simultaneously, are to be in one mode of operation.speciiically read into all examples in either or both of the processsteps.

Carrying on the process in either or both oi the steps in the presenceof catalytic materials has the eiect of smoothing out the operation,

shortening the time necessary for toxicity induction and/or makingoperations permissible at lowered temperatures. The most eiectivecatalysts are silicious materials, activated carbon, halogens andderivatives thereof cellulosic materials, syntheticgels and the oxides,suldes and-carbonates of metals.

I claim:

1. In the production of a preservative wood impregnant from the mixtureof petroleum frac.- tions boiling preponderantly above 270 C.characterized by a substantial percentage of i materials of cyclicstructure content andinherent but inhibited toxicity, comprises: heattreating tions at a temperature limits oi' about 370600C. while under arelatively high pressure ior'a period not in excess of about `30minutes; thereafter heat treating said material in entirety at atemperature selected between the limits above namedat a relatively lowpressure for a period not in excess o! about onev hour; inducingtoxicity into the materials under treatment by coordinating the time oitreatment in both periods of heating as to provide in the convertedmaterial less than about 30%.but more than about 5% saturation in the270-355" C. fraction; and segregating from the beneciated material anoil of the wood preservative type boiling preponderantly between 210 C.and 355 C., having an. end point at least as high as about 355 C. andsubstantial residual materials boiling above 315 C., and in the fraction27o-355 C. less than about 30% but more than about 5% saturates.

2. 'I'he process of claim 1 with inclusion of carrying on at least oneof the operational steps in the presence of an extraneous gas. Y

3. 'I'he process of claim 1 with inclusion oi carrying on the process inthe presence of catalytic material.

4. The process of claim 1 in which the segregated wood preservative is adistillate.

JACQUELIN E. HARVEY, JR.

